Phthaloperine derivatives



United States Patent ice 2,884,41 PnTHALoPER-Im: DERIVATIVES DonaldGraham Wilkinson, Manchester, England, assignor to Imperial ChemicalIndustries Limited, London, England, a eq mr qno G ea ita n No Drawing.Application October 5, 1956 SerialNo. 614,087

Claims priority, application Great Britain tobij 1 5 7 Claims. cl.260-2564) This invention relates to new colouring matters.

According to our inyention we provide new colouring Put e f th for ulawherein R is an alkyl, cycloalkyl, aralkyl, aryl or heterocyclicradical, A and B are substituted or unsubstituted hydrocarbon radicalswhich may be joined together to form a homocyclic or heterocyclic ringsystem, rt is 1, 2

ters which comprises heating a'primary alkyl, cycloalkyl, aralkyl, arylor heterocyclicamine with a polycyclic conipouud of the formula:

where A and B are substituted or unsubstituted hydrocarbon radicalswhich may be joined together to form a homocyclic or heterocyclic ringsystem, X'is NH or S, and the nuclei P and Q may carry substituents.

The substituents in the nuclei P and Q may be for example halogen atomsor alkyloxy groups or the nuclei may be substituted by an ethyleneradical connected to the carbon atoms in the peri positions.

The substituents on the radicals A and B and the ring system formed byjoining them, may be for example alkyl or alkyloxy radicals or halogenatoms. The primary amine may also carry such substituents.

As examples of suitable primary amines there may be mentionedthe'monoamines such as aniline, p-phenetidine, dehydrothio-p-toluidine,benzylamine, B-nitrafiili'ne, 4- nitraniline, l-naphthylamine,Z-naphthylamine and S-aminopyrene, the diarnines such as m orp-plienylenediamine, benzidine, tolidine, 1:5-naphthylenediamine,2:5-dichlorop-phenylenediamine, 2:'5-dimethyl-p-phenylenediamine, 4:;4'diaminodiphenylsulphone, 4:4 -'diaminostilbene, 3 8-diaminopyrene, 3IO-diaminopyrene, 2:7-diaminofluorenone, 3:8 diaminobenzofurane, 2:7diaminodiphenyle-nesulphone, 1:4 -,naphthylenediamine, 1:6naphthylenediamine, 1:7 naphthylenediamine, 2:6 naphthylenediamine, 2:7naphthylenediamine, 3:3 dimethoxy 4:4 diaminodiphenyl, 2:2 dinitro 4:4-diamino-diphenyl, 2 2-di (trifluoromethyl) 4 4-diami.nodiphenyl,3:3-dichlorobenzidine and azB-di-(4-aminophenX)-e.tha'ne and thetiiamines such as 1:3:5-triamino- Patented Apr. 28, 1959 v en e i ie a dia n are ed in s able proportions, colouring matters may be formed bylinkingtog ether two or more molecules of polycyclic compound. A

As suitable polycyclic compounds for use as starting materials in the plocess of our invention there may be mentioned for exampleIZ-iniino-phthaloperine and, l2,-

thiophthaloperinone, and their substitution products.

The polycyclic compounds used as starting materials in w h is S may be df o he QQI 'eSP- H HHE k o compound by methods known from the literatureor used in practice for IPl3Fi IB the oxygen atom of a carbonlil group,or the hydrogen atoms of a methylene group, by sulphur. Thus for examplelZ-thiophthaloperiuone may be made from phthaloperinone by the action ofphos- P m p a sfl ph de q f m hth o e n b h a in with sulphur.

The polycyclic compounds in which X is NH or S may be made by heating1:8-naphthylene diamine or a substituted 1:8-naphthylene diamine withadinitrile of the formula:

a-c- N 3-22501? a cya qthiq a c e imul Af' -C NII; B-o-cN or with acompound containing a 5-membered ring which n 9 1s Q i autom ti te ms at e em- 9 or with an alcohol addition productor .mercaptan additionproductthereof wherein A, B and X have the meaning given above and Y isa replaceable monovalent atom or group.

As an exam it e di flil t r m be m ntioned phthalonitrile and as anexample of a suitable cya t i dc h m y be m t n d ya o-thiobenzr m de-The group Y in the above formula may be for example O-alkyl, -SH,S-alkyl, NH or NHR where R; is a hydrocarbon vor substituted hydrocarbonradical. As specific examples of suitablering compounds which can beused to ,make the polycyclic compounds there may be mentionedl-imino-3-amino-isoindolenine, imino-thiciphthalimidine (a tautomericform of l-imino-3-mercapto isoindolenine), l imino 3ethylmercaptoisoindolenine, l-imino3-anilino-isoindolenine andl-phenylimino-3vanir lino-isoindolenine. As suitable alcohol andmercaptan addition products there may be mentioned l-imino-3z3dibenzylmercapto-isoindoline, 1-.imino-3 :3-di-ethoxy-isoe indoline and1-imino-3:3-(iethylene-dioxy)-isoindoline.

The reaction of the polycyclic compound with the primary amine may beconveniently brought about by heating the reagents together in anorganic solvent for exam! ple diphenylamine or nitrobenzene. It issometimes com venient to use the primary amine in the form of a salt forexample the hydrochloride. The new colouring matters may .then beisolated bycooling'and filtering the reaction mixture and washing anddrying .the residue on the filter. The product may be purified bycrystallisation if desired.

The new colouring matters of our invention are bright pigments of hightinctorial strength and high .stability to heat and light and they areespecially valuable for colour ing plastic materials which are to :bemoulded,- f or lac.- quer, paints and varnishes, and for .use in themass colouration of polymeric materials which are to be drawn" intofibres and films. They may also be used in the form of aqueousdispersions for dyeing artificial fibres.

1'- The invention'is illustrated but not limited by'the followingexamples in which the parts are by weight:

Example 1 i A mixture of 1 part of 12-imino-phtha1operine, 1 part ofp-phenetidine and 4 parts of diphenylamine is stirred at 280 C. for 1hour. The mixture is cooled to 100 C., 4- partsof nitrobenzene are addedand the mixture is then cooled to 20 C. The solid product in suspensionis filtered 01f, washed with benzene and dried. l2-p-ethoxyplienylimino-phthaloperine' is thus obtained in the form oforange needle shape'd crystals which melt at 264-266 C.

' Wh'enanalysed the product is found to contain 80.2% of carbon, 4.6% ofhydrogen and 10.8% of nitrogen (C H N O requires 80.1% of carbon, 4.9%of hydrogen and 10.8% of nitrogen).

Example 2 A mixture of 1 part of 12-imino-phthaloperine and 1 Whenanalysed the product is found to contain 83.1%

of carbon, 4.2% of hydrogen and 11.6% of nitrogen (C H N requires 83.5%of-carbon, 4.3% of hydrogen and 12.2% of nitrogen);

Example 3 In place of the 1 part of aniline hydrochloride used inExample 2 there are used 1.7 parts of the hydrochloride ofdehydrothio-p-toluidine. l2-p-(6-methylbenzthiazo-'lyl-2-)phenyliminophthaloperine is obtained in'the, form of redcrysta1s.-

Brown or red pigments are obtained when the following aminehydrochlorides are used in place of aniline hydrochloride in the processof Example 2.

, Amine hydrochloride Melting point Shade of pigment;

3-nitrai1iline -Q. 275280 O brown. t-nitraniline 266274 C reddish brown.I-naphthylamine .1. 240250 C".-. reddish brown. 3-aminopyrene 300-305 O-bluish re 4 methoxy 3 eminobenzene sulphon- 215-220? C yellowishdiethylamide. brown. Z-naphthylamine 260265 C regdlsh rown.2-naphthylamine- 6-sulphonamide'..- 290300 0 reddish .1 (dec.). brown.

Example 4 4 -trogen). The product is'a redpigment which is very stableto heat and light.

Example 5 In place of the 2 parts'of p-phenylene diamine used in Example.4, 2 parts ;of m-p'henylene diamine are used. A similar pigmentwhichmelts above 400 C. is obtained.

Example 6 Example 7 In place of the 2 parts of p-phenylene diamine usedin Example 4 there are used 4 parts of tolidine (3:3'-dimethy1-4:4-diamino-diphenyI)-.- The pigment so obtained melts at400405 C. and is similar in shade to the pigment of Example 6.

Example 8 uble in water and which melts-above 450 C. It is I A'mixture,of 15 parts of 12-imino-phthaloperine, 2

parts of p-phenylene. diamine and 40 parts of diphenylamine is stirredat 280 C. for 1 hour, during which time .ammonia is evolved. The mixtureis cooled, diluted with 50 parts of nitrobenzene and allowed to standfor 12 hours.- The 'solid in suspension is filtered off, washed withnitrobenzene 'and then with benzene and dried. The product iscrystallised from chloro naph thalene whenp-phenylene-bis-(12-imino-phthaloperine) is obtained in the form ofshining dark purplish red crystals-which melt above 430 C. When analysedthe product is fo'undto contain 82.7% of carbon, 4.3% of hydrogenand:13.5% of' nitrogen (C H N requires 82.4% of carbon, 3.9% of hydrogenand 13.7% of nivery stable to heat and light.

Brown or red pigments are obtained when the following diaminedihydrochlorides are used in place of 1:5-

naphthylene diamine dihydrochloride 1n the process of Example 8:

Diamlne dihydrochlorlde Melting point Shade of pigment2:5-diehloro-p-phenylenediamine.; above 450 0.. brownish red.2:5-dimethyl-p-phenylene diamine above 400 O red.

:3-dichl0ro-4:4-diarninodiphenyl 378380 brown.a:B-di(4-ami.nophenoxy)ethane..- 365-368 O orange brown.

-chloro-p-phenylenediamine 390393 C red. 1:4-naphthylenediamine.-.390-395 C bluish red. 1:6-naphthy1ened1amme above 440 C orange red.1:7-naphthylened1amme. 390393 C- red. 2:6-naphthylenediamine above 4500.- red. 2:7-naphthylenediaruine. 405-415 0..." orange red.2:2-dichloro-4:4-diarnino-diphenyl 390-395" G brown.2:2'-dimethyl-4:4-diamino-dipheny1 400-405 0... orange brown.2:2-dinitro-4:4-diami.no-diphenyl 370373 C- reddish brown.2:gfdliftriiiuoromethyl)-4:4-diamino- 375-378 0---- orange red.

- ip eny 3z3-di1nethoxy-4:4-diaminodiphenyl 397-408" O reddish brown.4:4-diaminodipheny1sulphone above 450 0.- orange. 4:4"diaminostilbeneabove 450 0.- orange red. 3:8-diaminopyrene above 450 0.- bluish red.3:10-diaminopyrene above 450 0.- brownish red. 2:7-diaminofiuorenoneabove 450 0.- reddish brown. 3:8-diaminodibenzofurane 424-434" 0.....reddish brown. 2:7-diaminodiphenylenesulphone above 440 0-- reddishbrown.

Example 9 A mixture of 20 parts of IZ-imino-phthaloperine, 4 parts of1:5-naphthylene diamine, 5 parts of p-toluene sulphonic acid and partsof chloronaphthalene is stirred at 220 C. for 4 hours. The mixture iscooled and the solid product in suspension is filtered off, washed withchloronaphthalene then with benzene, and finally with ethanol and dried.The product so obtained is identical with the first pigment described inExample 8.

-Example 10 .A mixture of 15 parts of 12-thio-phthaloperine, 2 parts ofpphenylenediamine and 40 parts of diphenylamine is stirred at 250 C. for4 hours. The mixture is cooled, 40 parts of nitrobenzene are added andthe crystalline solid in suspension is filtered ofi, washed withnitrobenzene then with benzene and finally with ethanol and dried. Theproduct so obtained is identical with that obtained by the process ofExample 4.

Example 11 Example 12 In place of the 5.5 parts of p-phenylenediaminedihydrochloride used in Example 11 there are used 5.5 parts ofm-phenylenediamine dihydrochloride. A red pigment is obtained whichmelts at 394-397 C.

Example 13 In place :of the 28 parts of chloro-12-imino-phthaloperineused in Example 11 there are used 28.5 parts ofnitro-12-imino-phthlaloperine. A violet-black crystalline product isobtained which melts above 440' C.

Example 14 A mixture of 30 parts of l2-imino-phthaloperine, 6.5 parts of1:3:5-triaminobenzene trihydrochloride and 180 parts ofchloronaphthalene is stirred at 200 C. for 2 hours and then at 220 C.for a further 2 hours. The mixture is cooled and the solid in suspensionis filtered ofi and washed with nitrobenzene, then with benzene andfinally with ethanol and dried. A dark brown crystalline product isobtained which melts above 400 C.

Example 15 In place of the 28 parts of chloro-lZ-imino-phthaloperineused in Example 11 there are used 27.5 parts of1:2-diphenyl-10-imino-perine. The violet pigment so obtained melts at360 C. with decomposition.

ii Example 16 A mixture of 27 parts of 12-imino-phthaloperine and 16parts of fi-phenylethylamine hydrochloride and 140 parts of nitrobenzeneis stirred at 220 C. for 3 hours. The mixture is cooled and filtered and40 parts of a light petroleum fraction which distills between C. C. areadded to the filtrates.

The precipitate so obtained is filtered OE and the solid is crystallisedfrom a light petroleum fraction which distills between C.l20 C.IZ-(fi-phenylethyD- imino-phthaloperine is thus obtained in small orangeneedle-shaped crystals or leaflets which melt at 152 C.

What I claim is:

l. Coloring matter of the formula:

wherein R is selected from the group consisting of monocyclicaryl-loweralkyl radicals and aryl radicals; n is an integer selected from thegroup consisting of one, two and three, Z represents the atoms necessaryto complete a benzene ring and the nuclei P and Q carry substituentsselected from the group consisting of hydrogen, halogen, alkoxy and theethylene radical connected to the carbon atoms in the peri positions.

2. 12-p-ethoxyphenylimino-phthaloperine.

3. 12-phenylimino-phthaloperine.

4. 12-p-(6-methylbenzthiazolyl-Z-)phenyl-iminophthaloperine.

5. p-Phenylene-bis- 12-imino-phthaloperine) 6. 1 :5 -naphthylene-bis-(12-imino-phthaloperine) 7. IZ-(B-phenylethyl)-imino-phthaloperine.

References Cited in the file of this patent Chemical Reviews, volume 35,pages 364 and 369 (1944).

1. COLORING MATTER OF THE FORMULA: